US1943176A - Cellulose solution - Google Patents
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- US1943176A US1943176A US563218A US56321831A US1943176A US 1943176 A US1943176 A US 1943176A US 563218 A US563218 A US 563218A US 56321831 A US56321831 A US 56321831A US 1943176 A US1943176 A US 1943176A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B1/00—Preparatory treatment of cellulose for making derivatives thereof, e.g. pre-treatment, pre-soaking, activation
- C08B1/003—Preparation of cellulose solutions, i.e. dopes, with different possible solvents, e.g. ionic liquids
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- This invention relates to new cellulose solutions and the application thereof for making various products chemically or mechanically, and to these products themselves.
- the invention is based on the observation that the liquefied quaternary ammonium salts for themselves or in presence of suitable liquids have the surprising property of dissolving cellulose with the formation of solutions of more or less viscosity.
- suitable liquids are above all anhydrous nitrogen-containing bases, such as anhydrous ammonia, or organic bases which do not decompose the quaternary ammonium salts, such as alkylamines (for example mono-, dior trimethylamine), aniline, monomethylaniline, dimethylaniline, pyridine, picoline, lutidine, technical pyridine bases, mixtures of these compounds, etc.
- the halides such as the chlorldes, bromides, and iodides are the most suitable.
- other salts such as for example sulfates, nitrates, or organic salts, such as formiates, acetates, etc.
- ammonium salts particularly those are further suitable which derive from halogen hydracid esters which contain up to 8 carbon atoms, such as benzyl chloride, chlorobenzyl chloride, ethyl, propyl or butyl chloride, or also from hexyl halides and octyl halides.
- halides such as for example with esters of halogen containing fatty acid, such as chloracetic ester or unsaturated products, such as allyl halides.
- esters of halogen containing fatty acid such as chloracetic ester or unsaturated products, such as allyl halides.
- the cellulose can be separated again from such solutions by means of suitable precipitating agents, so that, according to the selected conditions, artificial threads, films, artificial masses or the like can be obtained.
- the new cellulose solutions contain the cellulose in a very reactive form. They are, therefore, suitable for various chemical reactions, such as, for example, etherification or esterification; in particular they react very easily with acid anhydrides and acid chlorides.
- the cellulose derivatives thus obtained provided that they have not already been precipitated in the course of the reaction, can beseparated from the solution by means of suitable precipitating agents, so that these solutions also can be used under suitable conditions for producing artificial threads, films, artificial masses or the like.
- solutions of cellulose or its conversion products obtained according to the invention can be preserved for an unlimited time.
- the solutions can also be mixed in certain cases, if
- suitable anhydrous dlluents or other suitable additions.
- additions may be named, for example, substances having a reducing action, as, for instance, para-formaldehyde, glucose, lactose and the like; other suitable additions are substances, such as starch, dextrin and the like.
- Example 1 200 parts of anhydrous benzyl-pyridinium chloride are melted in a stirring vessel and heated to 110-115 C. At this temperature 10 parts of cellulose (preferably in the form of regenerated cellulose) are stirred in and the mixture is kept at the same temperature, with continuous stirring, until a homogeneous mixture is produced.
- cellulose preferably in the form of regenerated cellulose
- Example 2 100 parts of benzylpyridinium-chloride are mixed at 110-115 C. with 20 'parts of pyridine and to the homogeneous solution are added 6 parts of cellulose (preferably in the form of regenerated cellulose). Whilst continuously stirring, the mixture is kept at 115 0., whereby the cellulose dissolves with formation of a viscous liquid.
- Example 3 100 parts of dry pyridine, parts of benzylchloride and 11.2 parts of dry cellulose (preferably in the form of regenerated cellulose), are charged into a stirring vessel and the mixture is stirred and heated until the temperature rises, without further application of heat. Care is taken by cooling that the temperature does not exceed 115 C. Together with the formation of benzylpyridinium chloride the cellulose swells strongly. When no further spontaneous production of heat occurs, the mixture is maintained with continuous stirring at 115 C. whereby, according to the kind of cellulose used, the latter, after a period of some minutes up to several hours, is dispersed to form a highly viscous reddish-brown liquid.
- pyri.- dine another tertiary base or mixture of such bases may be used, for instance a mixture of '75 parts of pyridine and 25 parts of picoline.
- a mixture of '75 parts of pyridine and 25 parts of picoline By spinning the solution obtained, for instance in water, dilute acid or alcohol, cellulose threads of particular tenacity are obtained.
- Esample 4i 8 parts of dry bleached cellulose are intro water, cellulose is precipitated in coherent form.
- Example 100 parts of ethyl-pyridinium chloride are dissolved in 50 parts of pyridine, 7.5 parts of dry linters are introduced into the clear solution at 90-95 C. and the mixture is stirredat this temperature.
- the cellulose quickly becomes swollen and forms a viscous mass which on further stirring passes into the form of a highly viscous, completely clear solution which is well adapted for being spun.
- the properties of the spun material may be improved my incorporating in the cellulose during the dissolving process additions, such as para-formaldehyde, glucose, lactose, starch, dextrin or the like.
- v cosity of the cellulose solution may be diminished as desired by raising the temperature at which dissolution occurs, or by prolonged heating of the mixture.
- Cellulose solutions are also obtained by substituting 32 parts of aniline or 37 parts of methylaniline for the 50 parts of pyridine.
- Example 6 parts of monochloracetic acid ethyl ester and 100 parts of pyridine are heated whilst stirring to 90-100 C. until the formation of the pyridinium-chloracetic acid ethyl ester is completed; when reaction commences, care is taken to cool the mixture so that its temperature does not rise substantially above the aforesaid value.
- Example 7 To a cellulose solution of 5 per cent strength, made as described in Example 3, are added, after cooling the solution to about C. 3 molecular proportions (calculated on the cellulose) of acetic anhydride. After a short time the temperature rises gradually; preferably it is not allowed to rise above 90 C.
- the product obtained is completely soluble in tetrachlorethane. It may be used for making threads, artificial masses and the like.
- Example 8 To a solution of cellulose of 5 per cent strength made as described in Example 3 there are added at 90 C. a quantity of butyric anhydride corresponding with 3 molecular proportions icalculated on the cellulose). The mixture is heated,
- Example 9 A mixture of 1200 parts of dry pyridine and I 700 parts of benzylchloride is heated, while stirring, to -90 C. and, if necessary by cooling, the spontaneous heating of the mixture is so controlled that the temperature does not rise above 95 C. until the formation of the benzylpyridinium chloride is finished and a clear solution is produced.
- the pure white benzoyl-cellulose thus obtained is characterized by its solubility, being freely soluble in benzene, chloroform, tetrachlorethane and glacial acetic acid.
- Example 11 Into a solution of 8 parts of cellulose in 160 parts of a mixture of benzylpyridinium chloride and pyridine, made as described in Example 9, are introduced at 100 C. 5.2 parts of acetic anhydride, and after the reaction has proceeded for hour and the solution has cooled to 80 C., 14 parts of benzoyl chloride are further introduced. After the reaction has proceeded for another hour, the product is poured into aqueous alcohol and worked up as described in the preceding examples.
- the acetylbenzoylcellulose thus obtained is soluble in pyridine and ,in a mixture of tetrachlorethane and alcohol and forms a highly viscous solution.
- Example 12 Into a solution of 8 parts of cellulose in 160 parts of a mixture of benzylpyridinium chloride and pyridine, made as described in Example 9, there are introduced at 100 C. 20 parts of phthalic acid anhydride, and themixture is stirred for 1 hour at IOU-105 C. The light yellow-brown mass thus obtained is poured into 1 litre of water containing 5 per cent of pyridine, whereby the product which at first separates becomes completely dissolved. By acidifying the solution cellulose phthalic acid ester is precipitated in the form of a feebly yellowish flocculent mass, which is filtered by suction and washed with water. After it has been dried it is extracted with acetone.
- the cellulose phthalic acid ester which remains undissolved is an easily pulverized mass, which dissolves easily in weak alkalies, such as sodium carbonate or dilute ammonia, with formation of moderately viscous solutions, which are clear.
- the dried product is insoluble in organic solvents, such as acetone, alcohol, tetrachlorethane or benzene. It is freely soluble in aqueous pyridine.
- Example 13 Into a solution of 8 parts of cellulose in 160 parts of a mixture of benzylpyridinium chloride and pyridine, made as described in Example 9, are introduced at 110 C., 20 parts of well dried isatoic acid anhydride and the mixture is stirred at the said temperature for 20 hours. The mixture is then poured into much water. The product separates in the form of a slowly solidifying yellowish mass, which is comminuted and dissolved in cold sulphuric acid of 5-10 per cent strength.
- the solution which may be filtered, if necessary, is then made alkaline with sodium carbonate, whereupon the cellulose anthranilic acid ester separates in the form of a swollen pulverulent mass, which is filtered, washed with water and dried.
- ester thus obtained is insoluble in organic solvents but dissolves in dilute aqueous mineral acids to solutions which are opaque and foam strongly.
- Such solutions can be diazotized and coupled with suitable components for producing azodyestufis.
- Example 14 Into a solution of 8 parts of cellulose in 160 parts of a mixture of benzylpyrldinium chloride and pyridine, made as described in Example 9, are
- the cellulose-triphenylrnethyl ether thus obtained is a pure while brittle mass which dissolves in pyridine but is sparingly soluble in chloroform.
- esterification of the cellulose by means of the acylating agents named in Examples 9-14 may also be conducted in like manner with the use of the solutions of cellulose described in Examples 4-6.
- a manufacture of solutions of cellulose by dissolving cellulose in a solution, in a liquid base containing nitrogen whose dissociation constant at 25 C. is smaller than 7.5 X 10- of a quaternary ammonium halide obtained by addition of an aralkyl halide containing 'not more than 8 carbon atoms to pyridine.
- a manufacture of solutions of cellulose by dissolving cellulose in a solution, in a'liquid base containing nitrogen whose. dissociation constant at 25 C. is smaller than 7.5x 10- of a quaternary ammonium halide obtained byaddition of an alkyl halide containing at the most 5 carbon atoms to pyridine.
- a manufacture of solutions of cellulose by dissolving cellulose in a solution, in a tertiary base consisting of the mixture of the technical pyridine base, of a quaternary ammonium halide obtained by addition of an alkyl halide containing at the most 5 carbon atoms to pyridine.
- Solutions of an alkylpyridinium halide obtained by addition of an alkyl halide containing at the most 5 carbon atoms to pyridine, and of cellulose in a liquid base containing nitrogen whose dissociation constant at 25 C. is smaller than '7.5 10- 18.
Description
Patented Jan. 9, 1934 UNITED STATES CELLULOSE SOLUTION Charles Graenacher, Basel, Switzerland, assignor to Society of Chemical Industry in Basic,
Basel, Switzerland No Drawing. Application September 16, 1931,
Serial No. 563,218, and in Switzerland September 27, 1930 21 Claims.
This invention relates to new cellulose solutions and the application thereof for making various products chemically or mechanically, and to these products themselves.
The invention is based on the observation that the liquefied quaternary ammonium salts for themselves or in presence of suitable liquids have the surprising property of dissolving cellulose with the formation of solutions of more or less viscosity. Such liquids are above all anhydrous nitrogen-containing bases, such as anhydrous ammonia, or organic bases which do not decompose the quaternary ammonium salts, such as alkylamines (for example mono-, dior trimethylamine), aniline, monomethylaniline, dimethylaniline, pyridine, picoline, lutidine, technical pyridine bases, mixtures of these compounds, etc.
Among the ammonium salts the halides, such as the chlorldes, bromides, and iodides are the most suitable. There may also be used other salts, such as for example sulfates, nitrates, or organic salts, such as formiates, acetates, etc. Among the ammonium salts particularly those are further suitable which derive from halogen hydracid esters which contain up to 8 carbon atoms, such as benzyl chloride, chlorobenzyl chloride, ethyl, propyl or butyl chloride, or also from hexyl halides and octyl halides. Useful results may however also be obtained with other halides, such as for example with esters of halogen containing fatty acid, such as chloracetic ester or unsaturated products, such as allyl halides. The cellulose can be separated again from such solutions by means of suitable precipitating agents, so that, according to the selected conditions, artificial threads, films, artificial masses or the like can be obtained.
The new cellulose solutions contain the cellulose in a very reactive form. They are, therefore, suitable for various chemical reactions, such as, for example, etherification or esterification; in particular they react very easily with acid anhydrides and acid chlorides. The cellulose derivatives thus obtained, provided that they have not already been precipitated in the course of the reaction, can beseparated from the solution by means of suitable precipitating agents, so that these solutions also can be used under suitable conditions for producing artificial threads, films, artificial masses or the like.
The solutions of cellulose or its conversion products obtained according to the invention can be preserved for an unlimited time. The solutions can also be mixed in certain cases, if
necessary, with suitable anhydrous dlluents or other suitable additions. As such additions may be named, for example, substances having a reducing action, as, for instance, para-formaldehyde, glucose, lactose and the like; other suitable additions are substances, such as starch, dextrin and the like.
The following examples illustrate the invention, the parts being by weight:-
Example 1 200 parts of anhydrous benzyl-pyridinium chloride are melted in a stirring vessel and heated to 110-115 C. At this temperature 10 parts of cellulose (preferably in the form of regenerated cellulose) are stirred in and the mixture is kept at the same temperature, with continuous stirring, until a homogeneous mixture is produced.
Example 2 100 parts of benzylpyridinium-chloride are mixed at 110-115 C. with 20 'parts of pyridine and to the homogeneous solution are added 6 parts of cellulose (preferably in the form of regenerated cellulose). Whilst continuously stirring, the mixture is kept at 115 0., whereby the cellulose dissolves with formation of a viscous liquid.
Example 3 100 parts of dry pyridine, parts of benzylchloride and 11.2 parts of dry cellulose (preferably in the form of regenerated cellulose), are charged into a stirring vessel and the mixture is stirred and heated until the temperature rises, without further application of heat. Care is taken by cooling that the temperature does not exceed 115 C. Together with the formation of benzylpyridinium chloride the cellulose swells strongly. When no further spontaneous production of heat occurs, the mixture is maintained with continuous stirring at 115 C. whereby, according to the kind of cellulose used, the latter, after a period of some minutes up to several hours, is dispersed to form a highly viscous reddish-brown liquid. Instead of the pyri.-, dine another tertiary base or mixture of such bases may be used, for instance a mixture of '75 parts of pyridine and 25 parts of picoline. By spinning the solution obtained, for instance in water, dilute acid or alcohol, cellulose threads of particular tenacity are obtained.
Esample 4i 8 parts of dry bleached cellulose are intro water, cellulose is precipitated in coherent form.
Example 100 parts of ethyl-pyridinium chloride are dissolved in 50 parts of pyridine, 7.5 parts of dry linters are introduced into the clear solution at 90-95 C. and the mixture is stirredat this temperature. The cellulose quickly becomes swollen and forms a viscous mass which on further stirring passes into the form of a highly viscous, completely clear solution which is well adapted for being spun. The properties of the spun material may be improved my incorporating in the cellulose during the dissolving process additions, such as para-formaldehyde, glucose, lactose, starch, dextrin or the like. v cosity of the cellulose solution may be diminished as desired by raising the temperature at which dissolution occurs, or by prolonged heating of the mixture. Cellulose solutions are also obtained by substituting 32 parts of aniline or 37 parts of methylaniline for the 50 parts of pyridine.
Example 6 parts of monochloracetic acid ethyl ester and 100 parts of pyridine are heated whilst stirring to 90-100 C. until the formation of the pyridinium-chloracetic acid ethyl ester is completed; when reaction commences, care is taken to cool the mixture so that its temperature does not rise substantially above the aforesaid value.
10 parts of finely comminuted dry cellulose regenerated from viscose are introduced into the yellow solution of pyridinium chloracetic acid ethyl ester in pyridine thus obtained, and the whole is stirred at 105-1l0 C. until the cellulose is completely dissolved; this operation requires about one-half to one hour. There is thus obtained a brown viscous solution of cellulose which can be spun in water to threads which are scarcely coloured.
Example 7 To a cellulose solution of 5 per cent strength, made as described in Example 3, are added, after cooling the solution to about C. 3 molecular proportions (calculated on the cellulose) of acetic anhydride. After a short time the temperature rises gradually; preferably it is not allowed to rise above 90 C.
While continuously stirring, the temperature of the mixture is kept for 1 hour at 8090 C., and the mixture is then poured into water and the separated acetyl cellulose washed with water and alcohol.
The product obtained is completely soluble in tetrachlorethane. It may be used for making threads, artificial masses and the like.
Example 8 To a solution of cellulose of 5 per cent strength made as described in Example 3 there are added at 90 C. a quantity of butyric anhydride corresponding with 3 molecular proportions icalculated on the cellulose). The mixture is heated,
The viswhile continuously stirring, for 4 hours at 90- 95 C. and then poured into alcohol. The butyryl cellulose separates in the form of a fine powder, which is filtered by suction and boiled with alcohol for purification. The product is soluble in tetrachlorethane and in pyridine toa clear solution and forms a highly viscous solution.
Example 9 A mixture of 1200 parts of dry pyridine and I 700 parts of benzylchloride is heated, while stirring, to -90 C. and, if necessary by cooling, the spontaneous heating of the mixture is so controlled that the temperature does not rise above 95 C. until the formation of the benzylpyridinium chloride is finished and a clear solution is produced.
Into the pyridine solution of the benzylpyridinium chl'oride thus produced are introduced 100 parts of finely subdivided regenerated cellulose and the mixture is stirred, while the temperature rises to 110 C until a homogeneous cellulose solution is produced.
Into this solution, cooled to C. are run 320 parts of fused benzoic acid anhydride and the whole is stirred for 2-3 hours at 90-100 C. There is formed a brownish, homogeneous solution capable of being drawn into threads. This solution is poured into methylalcohol, and then the separated benzoyl-cellulose is extracted with methyl alcohol. The benzoyl-cellulose thus obtained differs in solubility according to the kind of cellulose used; the solubility is increased by prolonged heating of the product in the solution in which the reaction occurred. From the benzoyl-cellulose thus obtained there may be made clear elastic films which are not brittle. Excellent threads may also be obtained by spinning the product.
' Emample 10 Into a solution of 8 parts of cellulose in 160 parts of a mixture of benzylpyridinium chloride and pyridine, made as described in Example 9, are introduced at 70 C., 22 parts of benzoylchloride. The mixture is heated spontaneously and care is taken, by a suitable cooling, that the temperature does not rise above 90 C. After the reaction has proceeded for A hour, the mass is poured into methylalcohol and the pulverulent benzoyl-cellulose which separates is filtered by suction and extracted with methylalcohol.
The pure white benzoyl-cellulose thus obtained is characterized by its solubility, being freely soluble in benzene, chloroform, tetrachlorethane and glacial acetic acid.
Example 11 Into a solution of 8 parts of cellulose in 160 parts of a mixture of benzylpyridinium chloride and pyridine, made as described in Example 9, are introduced at 100 C. 5.2 parts of acetic anhydride, and after the reaction has proceeded for hour and the solution has cooled to 80 C., 14 parts of benzoyl chloride are further introduced. After the reaction has proceeded for another hour, the product is poured into aqueous alcohol and worked up as described in the preceding examples.
The acetylbenzoylcellulose thus obtained is soluble in pyridine and ,in a mixture of tetrachlorethane and alcohol and forms a highly viscous solution.
Example 12 Into a solution of 8 parts of cellulose in 160 parts of a mixture of benzylpyridinium chloride and pyridine, made as described in Example 9, there are introduced at 100 C. 20 parts of phthalic acid anhydride, and themixture is stirred for 1 hour at IOU-105 C. The light yellow-brown mass thus obtained is poured into 1 litre of water containing 5 per cent of pyridine, whereby the product which at first separates becomes completely dissolved. By acidifying the solution cellulose phthalic acid ester is precipitated in the form of a feebly yellowish flocculent mass, which is filtered by suction and washed with water. After it has been dried it is extracted with acetone. The cellulose phthalic acid ester which remains undissolved is an easily pulverized mass, which dissolves easily in weak alkalies, such as sodium carbonate or dilute ammonia, with formation of moderately viscous solutions, which are clear. The dried product is insoluble in organic solvents, such as acetone, alcohol, tetrachlorethane or benzene. It is freely soluble in aqueous pyridine.
Example 13 Into a solution of 8 parts of cellulose in 160 parts of a mixture of benzylpyridinium chloride and pyridine, made as described in Example 9, are introduced at 110 C., 20 parts of well dried isatoic acid anhydride and the mixture is stirred at the said temperature for 20 hours. The mixture is then poured into much water. The product separates in the form of a slowly solidifying yellowish mass, which is comminuted and dissolved in cold sulphuric acid of 5-10 per cent strength. The solution, which may be filtered, if necessary, is then made alkaline with sodium carbonate, whereupon the cellulose anthranilic acid ester separates in the form of a swollen pulverulent mass, which is filtered, washed with water and dried.
The ester thus obtained is insoluble in organic solvents but dissolves in dilute aqueous mineral acids to solutions which are opaque and foam strongly. Such solutions can be diazotized and coupled with suitable components for producing azodyestufis.
Example 14 Into a solution of 8 parts of cellulose in 160 parts of a mixture of benzylpyrldinium chloride and pyridine, made as described in Example 9, are
. alcohol, whereupon the cellulose ether separates first as a soft fibrous mass, which soon becomes hard and brittle. It is coarsely pulverized, extracted with methylalcohol and dried.
The cellulose-triphenylrnethyl ether thus obtained is a pure while brittle mass which dissolves in pyridine but is sparingly soluble in chloroform.
It will be understood that the esterification of the cellulose by means of the acylating agents named in Examples 9-14 may also be conducted in like manner with the use of the solutions of cellulose described in Examples 4-6.
Quite generally, it is recommended that the operations for making the cellulose solutions and cellulose derivatives be conducted with the exclusion of air or in presence of an inert gas.
Inall these examples it is indifferent whether the pyridine used as solvent is in the form of a pure or in the form of a dry technical pyridine.
in the presence of a liquid base containing nitro gen whose dissociation constant. at 25 C. is smaller than 7.5 10* 3. A manufacture of solutions of celulose by dissolving cellulose in a solution, in a liquid base containing nitrogen whose dissociation constant at 25 C. is smaller than 7.5 X 10*, of a quaternary ammonium halide obtained by addition of a halogen hydracid ester of an alcohol containing not more than 8 carbon atoms to a tertiary amine of the pyridine series.
4. A manufacture of solutions of cellulose by dissolving cellulose in a solution, in a liquid base containing nitrogen whose dissociation constant at 25 C. is smaller than 7.5 X 10- of a quaternary ammonium halide obtained by addition of an aralkyl halide containing 'not more than 8 carbon atoms to pyridine.
5. A manufacture of solutions of cellulose by dissolving cellulose in a solution, inpyridine, of the quaternary ammonium chloride obtained by addition of benzyl chloride to pyridine.
6. A manufacture of solutions of cellulose by dissolving cellulose in a solution, in a'liquid base containing nitrogen whose. dissociation constant at 25 C. is smaller than 7.5x 10- of a quaternary ammonium halide obtained byaddition of an alkyl halide containing at the most 5 carbon atoms to pyridine.
7. A manufacture of solutions of cellulose by dissolving cellulose in a solution, in a tertiary base consisting of the mixture of the technical pyridine base, of a quaternary ammonium halide obtained by addition of an alkyl halide containing at the most 5 carbon atoms to pyridine.
.8. A manufacture of solutions of cellulose by dissolving cellulose in a solution, in a liquid base containing nitrogen whose dissociation constant at 25 C. is smaller than 7.5 10 of the quaternary ammonium chloride obtained by addition of ethyl chloride to pyridine.
9. A manufacture of solutions of cellulose by dissolving cellulose in a solution, in pyridine, of
the quaternary ammonium chloride obtained by addition of ethyl chloride to pyridine.
10. A manufacture of solutions of cellulosev by dissolving cellulose in a solution, in ammonia, of the quaternary ammonium chloride obtained by addition of ethyl chloride to pyridine.
11. As a new composition of matter solutions containing, on the one part, quaternary ammonium salts obtained by addition of a halogen hydracid ester of an alcohol containing not more than 8 carbon atoms to a tertiary amine of the pyridine series, and, on the other part, cellulose.
12. As a new composition of matter solutions of quaternary ammonium salts obtained by addition of a halogen hydracid ester of an alcohol containing not more than 8 carbon atoms to a tertiary amine of the pyridine series, and celludissociation 13. Solutions or cellulose in a solution, in a liquid base containing nitrogen whose dissociaconstant at 25 C. is smaller than tion constant at 25 C. is smaller than '7.5X10- of a quaternary ammonium halide itself obtained from a tertiary base of the pyridine series and an aralkyl halide containing not more than 8 carbon atoms.
14. Solutions of an aralkylpyridinium halide} 16. Solutions of an aralkylpyridinium halide, obtained by addition of an aralkyl halidecontaining not more than 8 carbon atoms to pyridine, and of cellulose in' pyridine.
17. Solutions of an alkylpyridinium halide, obtained by addition of an alkyl halide containing at the most 5 carbon atoms to pyridine, and of cellulose in a liquid base containing nitrogen whose dissociation constant at 25 C. is smaller than '7.5 10- 18. Solutions of ethylpyridinium chloride and of cellulose in a base selected from the group consisting of pyridine, ammonia and aromatic amines of the benzene series.
19. Solutions of ethylpyridinium chloride and of cellulose in pyridine.
20. Solutions of ethylpyridinium chloride and of cellulose in ammonia.
21. Solutions of ethylpyridinium chloride and of cellulose in aniline.
CHARLES GRAENACHER.
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